Superbased barium containing lubricants



United States Patent Oflice 3,1 'Zfi,88l Patented Feb. 23, 1965 i 3,170,881 r SUPERBASED BARIUM CONTAINING a LUBRIQANTS VnnderveerVoorhees, Los Altos, Calif., assignor to Bray @il Company, Los Angeles, (Ialfifl, a limited partnership of tlalifornia J v No Drawing. Filed July 20, 1962, Ser. No. 2ll,37

' 8 Claims. (Cl. 252-327):

i This application is a continuation in part of application Serial No. 7 94,531 filed February 20, 1959, and now abandoned. V p

This invention relatesto a process of making lubricating oils and particularly lubricating oils containing barium compounds.- The process relates still more particularly to a method of introducing oil soluble barium compounds into hydrocarbon lubricating oils whereby the barium compounds are retained in the lubricating oil in a stable transparent dispersion in such a fine state of division'that the oil is readily filtera'ble. The invention also relates to a method of dispersing basic barium compounds in lubrieating oils thereby giving the oil a high alkali reserve and.

pounds in combination with oil soluble anionic detergents such aslthe barium salts of. sulfonatesfland phosphonates. Thelatter may be derived from the treatment of organic materials with phosphorous sulfides,. particularly P 8 Anionic, oil soluble detergents of the sulfonate type are well known in the art as described in the patent of Bray U.S. 2,689,221.

In the preparation of lubricating oil additives by the action of phosphorous sulfides such as phosphorous trisulfide and phosphorous pentasulfide, it has been the practice to neutralize the phosphonated products with various bases such as potassium hydroxide and barium hydroxide, thereby providing oil soluble compounds which 'ar'e valuable in lubricating oilsfor the purpose of preventing oxidation and sludging; These products are well known detergents and havebeen used widely in crankcase oils for the lubrication of internal combustion engines where they prevent the separation of sludge andreduce the oxidation of the oil, particularly where it comes into contact with hot surfaces such as pistons" and cylinder walls. It-has been'found desirable toincrease the alkali reserve of these additives by incorporating additional barium hydroxide or carbonate in various ways. The amount of barium hy droxide', however, which can be introduced, has heretofore mer having a wide range of molecular weights. I find that when employing products of high molecularweight, the V finished product will have the effect of improving the tively narrow molecular weight fractions or a mixed polyviscosity index of the lubricating oilto which it is added. Olefins suitable for producing these polymers are propylene, butylene, amylene, and the like. These monomers are conveniently polymerized by the action of catalysts such as BF AlCl and the like, in a manner well known to the art.

Other materials may be employed as starting materials for my process. For example; unsaturated hydrocarbons produced by cracking paralfin wax, and in general, any unsaturated hydrocarbon of suitable molecular weight and upwards of 20 carbon atoms.

To the olefin polymer starting material is added from 5 to 20%, usually aboutv 10-15%, of a phosphorous sulfide, preferably P 8 in the form of a powder or granules. Thereaction mixture is then heated in the absence of air to protect it from oxidation forwhich purpose a gas blanket of carbon dioxide is satisfactory. Goodagitationis required to maintain the phosphorous sulfide in suspension in the oil during the heating, and the temperature is held range of about 700 to 1500. These polymers canbe relahours. Usually, a reaction time of five hours at 300 F. is sufi'icient. Hydrogen sulfide is evolved in the reaction.

' -When the reaction mass is sufficiently cooled, it is con-- venient, although not necessary, to add a suitable diluent to reduce the viscosity of the intermediate product. For thispurpose, an equal volume of petroleum naphtha boiling in the range of 200 to 300 F; can be added. After settling for aperiod 'of time-for example, a few hours to one daythe unreacte'd phosphorous sulfide is largely settled to the bottom of the reaction vessel and .the intermediate oil can then be decanted into another vessel where it is subjected to the action of steam for the purpose of.

hydrolyzing the intermediate phosphorous-sulfur compounds which have been produced by interaction of the sulfide with the hydrocarbon. At this stage, hydrogen sulfide is liberated and must be disposed .of. Phosphoric acid "is also produced during the hydrolysis and for this reason it is necessary-to use acid resistantfequipment for the hydrolysis stage of the process. A glass lined steel tank issuitable, whereas in the first stage of the process I can use aluminum equipment which is resistant to the ac tion of sulfur and the thioacids which are pro'ducedby the P 8 reaction do not-attack the aluminum in the-absence of water.

The hydrolysis stage can be conveniently carried out at atemperature of about 300350 F. for a period of one to five hours. During the hydrolysis, the naphtha which was present in the stock from the first stage is distilled oil? and recovered. i

' After hydrolysis, the productis extracted with water to remove the water soluble acids, particularly phosphoric oil hot and it may be diluted at this point by adding a suitable light lubricating oil such as a refined 100 neutral oil. Refined distillate lubricating oils having viscosities in the range of about 60 to 200 SSU at 100 F. are suitable blending agents providing the volatility is not too low to interfere with the flash point specification of the finished product. The amount of dilution oil can suitably to about one-half to two parts by weight per part of olefin polymer starting material, and for most purposes dilution with an equal weight of blending oil is satisfactory. Naphtha can also be added to reduce viscosity and facilitate washing. The washed diluted phosphonated product is now ready for the neutralization step of the process which can be done with alkali or alkaline earth metal hydroxides as well known in the art. This is accomplished for example by adding a hot aqueous solution of barium hydroxide in excess of that required for reacting with all the phosphonic acids in the oil, an excess of about to 50% being desirable. The oil is thoroughly boiled with the barium hydroxide solution and the temperature raised to about 320 F. to complete the neutralization, although a lower temperature can be used for alonger period of time. The neutralization can also be accelerated by the addition of an alcohol such as butyl alcohol, which serves as a contacting agent. The neutralized product is separated from excess barium hydroxide, either by washing with water and alcohol or filtration, in which it may be desirable to use a filter aid such as Filter Cel, which is a well known infusorial earth. The neutralized oil is then thoroughly dried, if necessary by heating to a temperature of 325 to 350 F., or by subjecting it to the stripping action of naphtha vapor or other drying gas.

Super basing stage At this stage of the process, the neutralized phosphonated oil will usually have an alkali number of about to when titrated, using methyl orange as an indicator. It is very desirable to increase the alkalinity to a higher value for the purpose 'of neutralizing acids encountered in the use of the lubricating oil. Attempts to accomplish this by the use of excess barium hydroxide have usually failed, owing to the tendency of the barium compounds to form colloidal dispersions of coarse par-' ticles which can not be dissolved in lubricating oils to form transparent solutions. Such colloidal dispersions are commonly impossible to clarify by filtration, being either too coarse or too fine to be. satisfactorily filtered. The colloidal barium compounds have a tendency to seal over the surface of the filter with an impervious coating even where substantial quantities of filter aids are used. I have now discovered that barium hydroxide can be incorporated in the oil if it is added in the form of a barium oxide and methanol complex herein referred to as methanol-barium oxide. This complex can be conveniently made by reacting barium oxide and methanol, a reaction which takes place rapidly with evolution of much heat. On a large scale, it is necessary to supply cooling to prevent loss of methanol by distillation. At room temperature, e.g. 80 F., the concentration of barium in this complex may correspond to an alkali value of approximately 160. At higher temperatures, higher concentrations can be obtained. On cooling a warm solution, crystals of solid complex separate.

In order to produce an oil with any desired alkal value, it is only necessary to calculate the required amount of the methanol-barium oxide solution and add it to the oil. It is preferred that the oil be diluted with a suitable hydrocarbon solvent, for example, a petroleum naphtha having a boiling point of approximately 250 F. In one method of'operating, the methanol can be removed at this stage. On agitating and heating the mixture, the methanol is distilled off along with part of the naphtha and can be recovered and used again in the process.

The oil is next subjected to the action of a barium fixing agent which renders the barium insoluble in water, thereby producing a stable water resistant product. Most conveniently, this is done by treating with carbon dioxide gas in amounts suflicient to convert all the barium in the added methanol-barium oxide to barium carbonate. The exact form 'of the barium after carbonation is not fully understood but it is believed to be a complex carbonatephosphonate. Whatever the form, the product is a clear oil which, on heating to eliminate naphtha, thickens and sometimes congeals to a semi-solid mass somewhat resembling cup grease. A friable sponge is sometimes 'obtained, depending on conditions. This mass appears to be an oil-in-water type emulsion in which the barium phosphonate-carbonate complex forms the external phase. It is very difficult to beat this product without coagulation and decomposition on the heating surfaces if high temperatures are used. I have discovered that the intermediate product can be converted, apparently by reversal of emulsion, by mixing and heating with a small amount of water after which the product is a fluid oil which can be heated and concentrated by removal of solvent, water, etc. in the customary manner. The resulting product, for example, after dehydrating at 325 to 400 F., is a clear fluid oil usually red "or yellow in color, which can be filtered readily with a small amount of filter aid for purposes of final clarification. The end product may have an alkali value of 60 to milligrams KOH per gram equivalent or more. I

In the preparation of the methanol-barium oxide, I can use coarsely granular barium oxide and allow it to stand in contact with the methanol for a period of several hours or days during which time the methanol slurry reacts with the coarse granules, causing them to swell into a white gelatinous mass which is easily soluble in additional amounts of methanol. Commercial methanol is substantially anhydrous and can be used for the preparation of the methanol-barium oxide. I have found water to have an adverse effect on the reactionand it is desirable to avoid using methanol containing over one percent of water. Analyses show that commercially pure methanol contains less than.0.5% water. Analysis can be made by a'cloud point method using xylene as the water sensitive solvent viz:

To cc. sample of methanol add 100 cc. of xylene and mix. Adjust the temperature to 80 F. and titrate in water. If the methanol is water free, the cloud point will occur at 6.2 cc. of added water. Less water will be required with wet methanol, the amount being determined from the following calculation:

Percent water=6.2cc. water added This general method is described by Caley et al., Analytical Chemistry, vol. 33, p. 1613.

On standing, the methanol-barium oxide solution may develop a yellow color, particularly if the methanol is impure. There are indications that the methanol-barium oxide is a coordination compound in which the barium oxide and methanol are associated in a definite proportion.

The following examples will illustrate the process:

Example 1.--To 210 parts by weight 'of polybutene of 1200 molecular weight was added 60 parts of P 8 The mixture was rapidly agitated in an atmosphere of CO and the temperature increased to 380 F. in a period of ten minutes. The temperature was slowly increased to 400 F. in a period of one hour. Hydrogen sulfide was evolved during reaction and absorbed in alkali. The product was filtered to remove excess P 8 and hydrolyzed with steam at a temperature of 200 to 310 F. with further evolution of H 8. After two hours of hydrolysis, the reaction was substantially complete.

The product was washed with parts of water and an equal amount of aqueous secondary butyl alcohol. After settling for one hour, the water layer, approximately parts, was discarded. A test of the water layer showed substantial amounts of phosphoric acid. A second wash with 100 parts of aqueous secondary butyl alcohol hydrolysis and neutralization with Ba(OH) produce a clear solution of barium hydroxide in water.

The mixture was dehydrated with stirring to a temperature of 260 F. and then cooled and washed with water and sufiicient butyl alcohol to prevent emulsification. 100 parts of neutral oil was added to reduce the viscosity. The yield was 300 parts after filtering and the, product had an alkali value of 2.2 with phenol phthalein and 19 with methyl orange. It was a clear red oil with an ash value (sulfated) of 8.07%.

100 parts by weight of this oil was diluted with benzene and treated with 17 parts of methanol-barium oxide solution havingan alkali value of 130. On stirring, the mixture gave a cloudy emulsion into which carbon dioxide was passed while the temperature was raised to 180 F. distilling off the methanol. A solid spongy phase coagulated onthe heated surfaces of the vessel. Addition of further solventsuch as toluene and xylene helped to ex tend the dispersion but did not liquefy it, The product was a clear gelatinous mass at this stage. 50 parts of water was added to the mass after which the product rapidly lost its viscous, refractory consistency and became a thin oil which was dehydrated to 300 F. and filtered at a satisfactory rate. The clear red oil product had an alkali value of 1.5 with phenolphthalein and 80 with solution having an alkali value of 164. Also added was 20 partsof barium sulfonate having an alkali value of 68 and 100 parts of naphtha (250); Carbon dioxide was passed into the mixture until completely carbonated while warming. At 160 F. foaming resulted from evaporation of methanol and a brilliantly clear gel began to form as the solvent evaporated. Addition of 25 parts of water, rapidly decomposed the gel with the formation ot-fiuid oil which was dehydrated to 325 F. The clear oil was rapidly filtered to give a clear red oil product having an alkali value of 60 and an ash value of 17.57%.

Example 3.A phosphonate oil was made by action of P 8 on polybutene of 700 molecular weight followefl'lh by en blended with 100 neutral oil, it tested 5.4% ash and 20 alkali value. To 200 parts of this oil was added 10 parts by weight (5%) of a barium mahogany sulfonate of 68 oil of approximately 100 SSU viscosity at 100 F. To 'the blend was added parts of methanol-barium oxlde A.V., 200 parts of naphtha-250 boiling p'ointand 25 parts of secondary butyl-alcohoL. on boiling the solution with 50 partsof methanol-barium oxide solution 160 A.V.), the'solution became clear. CO was'passed in at a temperature of 150 F. to110 .F. as it cooled. In

twenty minutes the solution gelled, then 20 parts of water ble petroleum sulfonates' with barium, any well known mahogany sulfonate of thealkali or: alkaline earth metals may be used, such as sulfonates of barium, calcium, sodium, potassium, lithium, magnesium, etc. As an example, a calcium sulfonate of a preferentially oil soluble oxide as follows:

To 200 grams of a calcium sulfonate-lubricatingoil solution containingabout 30% sulfonate with a molecular weight of about 500 there was added 50 cc. petroleum naphtha, boiling point-400 F. To the solution was added with stirring, 100cc. ofa solution of methanolbarium oxide prepared by dissolving barium oxide in methanol (160 alkali value). CO was passed into the cloudy mixture while'warm. A layer of methanol was petroleum sulfonic acid was treated with methanol-barium formed on the surface, released by the action-ofthe CO;

on the complex. A gummy emulsion formed to a small extent on the sides of the container. added followed by heating to boiling. The gummy material rapidly dispersed as the emulsion phases were reversed or inverted. The oil was dehydrated to 325 F. and filtered rapidly. Tests of the. oil gave an alkali value of with methyl orange and 5 with phenolphthalein indi cators. Ash value (sulfated)21.l%. The original calcium sulfonate tested 8% .ash and 18 A.V. I

When the above experiment was repeated, omitting the CO stabilizing step,-the product had an alkali value .of only 21 (phenolphthale'in) and 26 (methyl-orange).

.t'ixamplev 5.'In.this run, .75 kg. of polybutene made up of a blend of equal amounts by weightof -butylene polymers of 750, 1200 and 1700 molecular weight, .was agitated in an aluminum vessel, with 1 kg. of' granular P 8 while heating to 410 F. under a blanket'of CO After 2.5 hours at thistemperature, the mass was cooled to 225 F. and 2 gallons of naphtha (250 boiling point) was added with stirring. Onstanding 24 hours, substan tially all unreacted P 8 had settled as a firmcake on the bottom. The oil was decanted into a glass enameled steel kettle and hydrolyzed with steam at 350 F. for about 2 hours, stripping olf the naphtha. It was again cooledand re-diluted withthe recoverednaphtha and 4 kg. of neutral oil to reduce viscosity. The oil solution was then extracted with a solution of 1 gallon aqueous secondary butyl alcohol (67% and -1 gallon water. After settling, the bottom layer was removed and it was again extracted with a solution of 1 gallon water and one-half gallon aqueous secondary butyl alcohol to removephos phoric acid which, if left in the oil, would produce insoluble barium phosphate later, in colloidal form, impossible to remove from the oil because ofthe powerful peptizing action of the phosphonate. I

The extractedoil was neutralized by mixing with a hot Water solution of Ba(OH made by adding slowly to hot water, 600 grams of BaO. The oil was then stripped of solvents and heated, with g ood agitation, to 300 F. 011 standing, the excessbarium hydroxide precipitated as a redmud. The oil was diluted with naphtha (250) and filtered to'remove all suspended matter, then heated to remove water. To the naphtha-oil solution was then added with stirring 3.5 kg. methanol-barium oxide solution and themethanol was distilled otf. It is desirable to employ a naphtha dilution of about 1:1 or 2:1, naphtha-oil ratio, to facilitate mixing and 'bariumiZingQ Carbon dioxide was then absorbed into' theoil with good.

agitation and the clear solution was treated, while warm,

7 with one liter of water. If allowed to cool, the solution may setto a solid gel, diflicult to handle.

The solution was then boiled to remove naphtha and watenheating to 340 F. to drive off all water. The hot oil was mixed with about 2% ofits weight of filter aid and-filtered. The clear, light red product had an alkali value of 68. y

. Example 5a.1n a turbine mixer was placed gm, ofa 40% solution ofcalcium mahogany sulfonate in lubricatingoil (alkali value17) and 250 cc. of V.M. and

P. naphtha. Then 150- cc. of a barium oxideanhydrous methanol solution (alkali value) was added and the mixture blended to a homogeneous emulsion which appeared to be a colloidalisol'ution.

On heating in a casserole, the solution congealed at-1 40 25 cc. of water was.

Start CO2 2 minutes 148 4 minutes 154 6 minutes 152 15 minutes 140 20 minutes 135 Terminated.

An attempt was made to filter the mixture on a suction funnel after addition of Hy-Flo filter aid, but it was found to be unfilterable, the liquid drying on the sides of the funnel to a tenacious varnish-like coating. It was then treated in a casserole with 25 cc. water, boiling vigorously and heating to 250 F. Some gelling was observed at this temperature, so the water treat was repeated, dehydrating again at 250 F. More V.M. and P. naphtha was added with filter aid and the solution filtered rapidly on a suction funnel. The clear filtrate was stripped free of naphtha at 340 F. giving a brilliantly clear oil, neutral to phenolphthalein Yield 99 grams. Alkali value 140 (methyl orange).

This example illustrates the importance of the water treating step in my process.

Example 6 .A polybutene of 700 molecular weight was reacted with 19% by weight of P S at 460 F. for twenty minutes under a blanket of illuminating gas to exclude air. The product, diluted with an equal amount of naphtha was filtered, then hydrolyzed with steam. The naphtha was removed and the hot oil, cut back'with 50% by weight of neutral 150 oil, was decolorized with filter clay at 300 F. The yellow oil was neutralized with barium hydroxide solution, dehydrated and filtered. Alkali value 2.8 (phenol-phthalein) and 41 (methyl orange), ash- 12.28%, phosphorous-1.54%, sulfur-1.33%.

Example 7.-A polybutene was treated with P S and neutralized with barium hydroxide as above to give a clear yellow oil having the following analysis:

Phos., percent 1.27 Sulf., percent 0.98 AshBaSO percent 11.45 Alkali value (methyl orange) 49 One hundred cc. of a solution of barium oxide in methanol (126 A.V.) was mixed with 100 cc. of commercial methanol containing about 0.2% water, then to the mixture was added 100 gm. of the above phosphonated oil and 250 cc. varnish makers andpainters naphtha. Mixing was done in a turbine mixer at moderate speed.

CO was then passed in at a rate of one liter per minute,

the temperature being noted as follows:

Start CO 102 2 min. 105 6 min. 111 10 min. 108 min. 102

Terminated.

The reaction mixture was transferred to a pan, diluted with 300 cc. of light naphtha and heated to 144 F. to eliminate methanol. The mixture formed a clear gel which was inverted by adding 100cc. water. The oil was dehydrated at 400 F., then filtered. It was opalescent and tested 139 alkali value (methyl orange)ash 22.01%.

. Example 8.This example shows that anhydrous methanol is unique in my process, the higher alcohols such as propanol being inoperative.

The sulfonate employed in these experiments was a commercial product prepared by sulfonation of solvent refined petroleum lubricating distillate of about 450 molecular weight. The sulfonated oil was neutralized with caustic soda, then purified and concentrated by treatment with water and butyl alcohol in the manner shown in US. Patent 2,689,221. The sodium sulfonate-oil product having a concentration of about 40 percent oil-free sulfonate, was then converted to barium sulfonate by metathesis with barium chloride solution, washed free of chloride and dehydrated in the presence of barium hydroxide, then filtered bright. The product tested as follows:

Ash, sulfated 20.6%. Barium; 11.75%. Ba conversion 97%. Alkali value 46 (phenolphthalein indicator). Alkali value 52 (methyl orange indicator).

Viscosity Fluid.

This oil was treated with barium oxide and CO in the presence of anhydrous methanol and also in the presence of isopropanol, under identical conditions as follows:

100 cc. of the alcohol was placed in a Waring turbine mixer and to this was added, while stirring, 35 grams of barium oxide-granulated (technical grade). Then was added 100 grams of the barium sulfonate-oil described above, and 200 cc. of petroleum naphtha-varnish makers and painters grade (VM & P). The mixer speed was adjusted to correspond to40 volts on a Power-stat regulator, Type 116 (Superior Electric Company). A stream of carbon dioxide gas generated from Dry Ice was then passed in at the rate of approximately one liter per minute and continued with stirring for thirty minutes. Temperatur'es were recorded as follows: I

The solution was filtered easily on a suction funnel to remove any unreacted barium oxide. The clear solution was then heated in a pan on an electric hot plate, stirring constantly, to evaporate the alcohol.

In the case of methanol, a thick gel formed at about which tended to burn on the bottom of the pan. With constant stirring, it was heated to then 50 cc. of water was added with rapid stirring. The gel became a grainy solid mush which broke to a liquid in about five minutes. It was heated to 350 to expel water and naphtha and the hot product oil was filtered easily using about two percent of I-ly Flo filter aid.

In the case of isopropanol, the filtered solution was heated to 190 with no gel formation. Heating was continued to 350, then the hot product oil was filtered with two percent of Hy Flo filter aid. Following are the analyses of both products:

certain specific examples, I-intend that it be not limited thereby but that it also include numerous variations. Thus, I may modify the hydrolysis step by conducting it in the presence of ammonia or a suitable amine such as morpholine, aniline, pyridine, butylamine, monoethanol amine, diethanol amine, and the like. On following the hydrolysis with barium,=hydroxid neutralization, the nitrogen bases, either amine or ammonia, are driven oh and recovered for re-use in the process.

I have described the use of sulfonates and phosphorous sulfide-olefine reaction product as dispersantsin my process but other oil soluble anionic surface active agents can be employed, such as the fatty acids of 16 carbon atoms or more and the naphthenic acids from petroleum. Surface active agents of 400 to 500 molecular weight and higher are generally most effective. In place of carbon dioxide as a stabilizing agent for the barium after treating with methanol-barium oxide, I may use various other stabilizing agents such as oxalic acid, sulfur dioxide, or other acid which forms with the barium a water insoluble compound. It is essential, however, to effect contact with the stabilizing agent in such a manner as to avoid formation of colloidal particles which cannot subsequently be removed by filtration. Thus particles in the range of 0.1

to 1 micron are peptized by the phosphonate or sulfonate and are not removed by filtration. The filtered oil is cloudy and of little value in commerce. Particles having dimensions less than the wave length of visible light are satisfactory. I can add the barium stabilizer, such as oxalic acid, in solution in an alcohol such as methanol, methyl isobutyl carbinol, hydroxethyl ether, etc.

The methanol can be distilled off from the mixture of barium oxide, oil and surface active agent, either before or after treating with the barium fixing agent such as C Since methanol has a low boiling point148 F.it is easily removed especially if a hydrocarbon solvent is present, lowering the boiling point still further. When gel formation is encountered, it is convenient to strip out methanol with vapors of a solvent naphtha, preferably one boiling in the range of about 200 to 300 F. Aromatic naphtha, such as xylene or toluene can be used but paraf- .finic naphtha such as varnish makers and painters naphtha methanol-barium oxide solution as hereinabove described.

In the first stage of the process, the reaction with P 8 can be accelerated by adding an aromatic hydrocarbon to the reaction mixture, thereby increasing the solubility coeflicient of the P 8 Naphthalene is effective for this purpose, in the proportion of 10 to 25% of the weight of the olefine starting material. It can be stripped from the reaction mass with steam and used again. Alkyl naphthalene, particularly methyl naphthalene, is also useful. The term methanol barium oxide employed in the claims means the reaction product of methanol and barium oxide.

Having thus described my invention, what I claim is: l. The process of making clear superbased barium containing lubricating oils which comprises (1) forming a clear substantially water-free solution in lubricating oil of a compound selected from the class consisting of "alkali and alkaline earth metal I salts of high .molecular weight oil-soluble sulfonic acids and of acids derived from reacting phosphorous sulfide with olefins of about 500 to 3,000 SSU 10 viscosity at 210 F. and hydrolyzing the product with a metal base,

(2) adding to .the resulting lubricating oil solution a substantially anhydrous methanol solution of barium oxide, 7

(3) agitating the mixture to form an emulsion,

(4) adding to the emulsion in the absence of water an acid which forms a water insoluble compound with barium,

(5) heating the resulting water-free mixture to distill methanol therefrom, thereby forming a gel,

(6) decomposing the resulting gel by the action of water, and

(7) dehydrating the mixture.

2. The process of making a clear superbased oil for lubrication of internal combustion engines from a clear, substantially water-free lubricating oil which contains dissolved therein a dispersant prepared by treating an olefinic hydrocarbon of about 500 to 1,500 molecular Weight with phosphorus pentasulfide, hydrolyzing the product and neutralizing the resulting acid product with a base selected from the class consisting of alkali and alkaline earth metal bases, which process comprises (1) mixing said dispersant-containing lubricating oil with a substantially anhydrous methanol solution of barium oxide, thereby forming an emulsion,

(2) treating the emulsion in the absence of water with an acidic stabilizing agent which forms a water insoluble compound with barium,

(3) heating the resulting water-free mixture to distill methanol therefrom, thereby forming a gel,

(4) then treating the mixture with water to break the gel, and

(5) dehydrating the resulting water-in-oil emulsion to produce the desired clear oil of high reserve alkalinity.

3. The process of claim 2 wherein the said stabilizing agent is carbon dioxide.

4. The process of claim 2 wherein the stabilizing agent is sulfur dioxide.

5. The process of incorporating barium into lubricating oil in the form of a transparent dispersion which comprises (1) forming, in lubricating oil, a solution of an oil soluble anionic surface active agent having a molecular weight of at least 500 selected from the class consisting of alkali and alkaline earth metal, oil soluble sulfonates and phosphonates derived from treatment of olefins with phosphorous sulfide and hydrolyzing the reaction product with a metal base,

(2) mixing with said solution, in the substantial absence of water, a methanol solution of barium oxide,

(3) converting the resulting anhydrous dispersion to a water resistant form by saturating it with carbon dioxide,

(4) heating the saturated anhydrous dispersion to distill methanol therefrom, thereby forming a gel,

(5) treating the gel with water to break the gel and form a fluid oil, and

(6) then dehydrating the fluid oil to form the desired superbased lubricating oil.

6. The process of claim 5 wherein said surface active agent is a compound of a preferentially oil soluble sulfonic acid.

7. The process of claim 5 wherein said surface active agent is an oil soluble compound derived from the treatment of an'olefin of about 500 to 3,000 'SSU. viscosity at 210 F., with phosphorus pentasulfide followed by hydrolysis and neutralization with a metal base.

8. The process of making transparent superbased barium containing lubricating 'oils which comprises 1) forming a water-free mixture from a solution of barium oxide in methanol and a lubricating oil solution of a preferentially oil soluble sulfonate of a metal selected from the class of alkali and alkaline References Cited by the Examiner (ziar h m eh d 1 1 UNITED STATES PATENTS agitating t e mixture an simu taneous y introducing carbon dioxide thereinto in the absence of n Wat, 5 2 956 018 10/60 0 l le et i 252- 27 (3) heating to distill methanol, thereby forming 21 3:021:25) 2/62 23,1 i

gummy emulsion, 3,027,325 3/62 McMillen et al. 25233 (4-) treating the gummy emulsion with Water and boil- FOREIGN PATENTS Zing to invert the emulsion, thereby pro ucmg 21 md 10 570,814 2/59 Canada.

(5) and thereafter dehydrating the oil by heating to DANIEL WY Prim ry Ex m ner. drive off the water. ALPHONSO D. SULLIVAN, Examiner. 

1. THE PROCESS OF MAKING CLEAR SUPERBASED BARIUM CONTAINING LUBRICATING OILS WHICH COMPRISES (1) FORMING A CLEAR SUBSTANTIALLY WATER-FREE SOLUTION IN LUBRICATING OIL OF A COMPOUND SELECTED FROM THE CLASS CONSISTING OF ALKALI AND ALKALINE EARTH METAL SALTS OF HIGH MOLECULAR WEIGHT OIL-SOLUBLE SULFONIC ACIDS AND OF ACIDS DERIVED FROM REACTING PHOSPHOROUS SULFIDE WITH OLEFINS OF ABOUT 500 TO 3,000 SSU VISCOSITY AT 210*F. AND HYDROLYZING THE PRODUCT WITH A METAL BASE, (2) ADDING TO THE RESULTING LUBRICATING OIL SOLUTION A SUBSTANTIALLY ANHYDROUS METHANOL SOLUTION TO BARIUM OXIDE, (3) AGITATING THE MIXTURE TO FORM AN EMULSION, (4) ADDING TO THE EMULSION IN THE ABSENCE OF WATER AND ACID WHICH FORMS A WATER INSOLUBLE COMPOUND WITH BARIUM, (5) HEATING THE RESULTING WATER-FREE MIXTURE TO DISTILL METHANOL THEREFROM, THEREBY FORMING A GEL, (6) DECOMPOSING THE RESULTING EL BY THE ACTION OF WATER, AND (7) DEHYDRATING THE MIXTURE. 